Vinyl-functionalized oxazolones (e.g., “azlactones”) represent a unique class of bifunctional monomers; the most widely studied monomer in this category is 2-vinyl-4,4-dimethyl-5-oxazolone (VDMO). VDMO, also commonly referred to as vinyl azlactone or vinyl azlactone, has been used in a number of acrylamide- and acrylate-based insoluble polymer supports for enzyme immobilization and affinity chromatography (see, for example, Coleman et al. (1990) J. Chromatography 512:345-363; Drtina et al. (1996) Macromolecules 29:4486-4489; and Hellmann et al. (2001) J. Polym. Sci., Part A: Polymer Chem.39:3677). Poly(VDMO) has also been grafted onto molded macroporous polymer monoliths (Peterson et al. (2002) J. Anal. Chem. 74:4081-4088; Xie et al. (1999) J. Biotechnol. Bioeng. 62:29-35). In addition, these materials can be used as effective amine scavengers for organic syntheses (Tripp et al. (2000) J. Org. Lett. 2:195-198; Tripp et al. (2001) J. Combi. Chem. 3:216-223).
There have been several reports regarding the traditional free radical copolymerization of VDMO using azo-initiators. However, VDMO has a tendency to homopolymerize relative to the comonomer, resulting in depletion of VDMO at low conversions. Consequently, the resulting product polymer is a complex mixture of copolymer chains having both a heterogeneous microstructure as well as a broad molecular weight distribution. The present invention overcomes these and other difficulties in the art, by providing methods for the synthesis of oxazolone-containing polymers having defined architecture and narrow polydispersity.